Emulsifiers and a process for the production of large particle size, homodisperse polymer dispersions using these emulsifiers

ABSTRACT

Reaction products of 1 mol of a cycloaliphatic diol corresponding to formula I 
     
         HO--R--OH                                                  I 
    
     with 2 mols cycloaliphatic carboxylic anhydrides corresponding to formulae II and/or III ##STR1## in which R is a cycloaliphatic hydrocarbon radical having 6 to 20 carbon atoms onto which the hydroxy groups are bonded directly or via methylene groups and X represents ##STR2## chemical bond --obtainable obtainable by fusion of the cycloaliphatic diol and the cycloaliphatic carboxylic anhydride in an inert gas atmosphere at temperatures of from 100° C. to 250° C., and the alkali and ammonium salts of these reaction products, and their use as emulsifiers.

This application is a divisional of Ser. No. 509,514 filed Apr. 16,1990, now allowed.

This invention relates to emulsifiers and to the production of largeparticle size, homodisperse polymer dispersions using these specificdispersion aids (emulsifiers) which show an unobvious effect.

In the context of the invention, "homodisperse" dispersions (latices)are those in which the latex particles have a narrow diameterdistribution. Average latex particle diameters are defined for instanceas average volume diameter DAV or as average number diameter DAN of theparticles as follows: ##EQU1## (c.f. DIN 53 206),

The DAV/DAN ratio may be regarded as defining uniformity.

"Large" particle size dispersions may be those wherein the averageparticle diameter DAN is from 150 to 600 nm and preferably from 250 to450 nm. Latices having a DAV/DAN ratio of <1.15 may be called"homodisperse".

It is known that large particle size polybutadiene latices are requiredfor the production of high-impact thermoplastic molding compounds (forexample high-impact polystyrene, ABS polymers). Basically, coarselydivided (rubber) latices may be prepared using standard emulsifiers bythe seed latex method (cr. Houben Weyl, Methoden der Organischen Chemie,Makromolekulare Stoffe, Part 1, 1961, Thieme Verlag Stuttgart, page339).

Emulsifiers based on the naturally occurring resin acids ("resin soaps")have been used for the production of polybutadiene latices,butadiene-styrene copolymer latices, polychoroprene latices. However,"resin soaps" promote the formation of new latex particles, so thatundesirable finely divided, even dimodal or polymodal latices areformed.

Accordingly, though resin soaps have proved to be suitable for theproduction of finely divided polybutadiene and butadiene-styrenecopolymer latices having favorable natural color and processibility,they are less suited to the production of homodisperse, large particlesize latices.

The present invention is based on the discovery that large particle sizelatices can readily be obtained by using special emulsifiers in thebatch emulsion polymerization, semicontinuous emulsion polymerizationand continuous seed emulsion polymerization processes known per se.

The present invention relates to reaction products of 1 mol of acycloaliphatic diol corresponding to formula I

    HO--R--OH                                                  I

with 2 mols cycloaliphatic carboxylic anhydrides corresponding toformulae II and/or III ##STR3## in which R is a cycloaliphatichydrocarbon radical containing 6 to 20 and preferably 6 to 15 carbonatoms, to which the hydroxy groups are attached directly or viamethylene groups and

X represents ##STR4## chemical bond which reaction products areobtainable by fusion of the cycloaliphatic diol and of thecycloaliphatic carboxylic anhydride in an inert gas atmosphere attemperatures of from 100° C. to 250° C. and to the alkali and ammoniumsalts of these reaction products.

The invention also relates to their use as emulsifiers.

Reaction products of 1 mol (I) and 2 mols (II) or of 1 mol (I), 1 mol(II) and 1 mol (III) are preferred.

The new reaction products (emulsifiers) are alkali or ammonium salts ofacidic resins which are obtained by reaction of 1 mol of acycloaliphatic diol with 2 mol of a cycloaliphatic anhydride or with ananhydride mixture, for example by reaction of 1 mol of a cycloaliphaticdiol with maleic anhydride and/or itaconic anhydride.

The reaction products according to the invention can be represented bythe following general formula

    Y.sub.1 --O--R--O--Y.sub.2                                 (IV)

in which the Y's independently represent ##STR5## in which X and R areas defined above.

In formula (IV), R is a cycloaliphatic radical with two bonds, a"spacer" for the two, preferably dimetrically opposite, hydroxyl groupsattached to the ring system either directly or via a methyl group.

The substituents R may be cycloaliphatic ring systems, for example, of6-membered or 5-membered and 6-membered optionally alkyl-substitutedrings. Such ring systems can readily be synthesized, for example, fromdienes and dieneophiles by the DIELS-ALDER reaction. Preferredsubstituents R are: ##STR6##

The diols required as starting product may be obtained in known mannerby hydroformylation of cyclic dienes or of saturated aldehydes oralcohols with subsequent reduction of the aldehyde group (cf. MethodicumChimicum, Kritische Ubersicht bewahrter Arbeitsmethoden und ihreAnwendung in Chemie, Naturwissenschaft und Medizin (Critical Review ofProven Methods and their Application in Chemistry, Natural Science andMedicine), Ed. F. Korte, G. Thieme Verlag, Stuttgart, 1975, pages 212 to215).

Other diols are obtained by hydrogenation of the corresponding aromaticcompounds such as, for example, hydroquinone or by addition of wateronto the corresponding diolefins.

Particularly suitable diols are 1,4-cyclohexanediol,1,4-bis-hydroxymethyl cyclohexane, bis-hydroxymethylhexahydro-4,7-methanoindane (commercially available as "TCD-Diol"produced by hydroformylation of dicyclopentadiene) (U.S. Pat. No.2,850,536), bis-hydroxymethylbicyclo-(4,3,0)-nonane, bis-hydroxymethylnorbornane, bis-hydroxymethyl cyclooctane.

The diols mentioned are generally isomer mixtures.

Anhydrides which may be reacted with the diols mentioned includehexahydrophthalic anhydride, tetrahydrophthalic anhydride,5-norbornene-2,3-dicarboxylic anhydride, norbornane dicarboxylicanhydride, maleic anhydride and itaconic anhydride.

The last two anhydrides are preferably reacted with the diols mentionedabove in combination with saturated anhydrides. Copolymerizableemulsifiers are obtained.

The diols may preferably be reacted with the anhydrides in bulk (in themelt). With small batches, the diol may be mixed with the anhydride andreacted in the melt. With larger batches, the molten components arepreferably added separately from one another to a melt of already formedreaction product. In most cases, it is also of advantage initially tointroduce the anhydride or anhydride mixture and than to add the diolthereto. In the production of asymmetrical emulsifier acids, it is evenpossible to introduce the diol first and then to add the anhydride offormula II and, lastly, maleic or itaconic anhydride.

The reaction may be accelerated by small quantities of a tertiary amine,such as triethylamine or tributylamine. The end of the reaction may berecognized by determination of the acid value of the melt and from thedisappearance of the anhydride band in the infrared spectrum. Thereaction mixtures may be characterized by their acid value and by GPCanalyses.

The reaction of the diols with the anhydrides is preferably carried outin an inert gas atmosphere at temperatures in the range from 100° to250° C. and preferably at temperatures in the range from 100° to 200° C.Nitrogen or argon is preferably used as the inert gas.

The pure substances (isomers), e.g. those corresponding to the formulaeshown in Table 1, do not have to be isolated from the reaction mixturesfor the use as emulsifiers in accordance with the invention. Thediolefins used for hydroformuylation may themselves consist of mixtures.For example, dicyclopentadiene consists of a mixture of cis- andtrans-Diels-Alder adduct. In the hydroformylation reaction, the numberof isomers is further increased so that the diols used for reaction withthe dianhydrides are generally mixtures of isomers. Accordingly, theformulae in Table 1, column 1, may be interpreted as isomer mixtures andthe molecular weight in column 2 is that of the isomer mixture.

On completion of the reaction and after volatile constituents,particularly excess anhydrides, have been removed by distillation orsublimation, the reaction mixtures formed during the reaction of cyclicdiols with the anhydrides mentioned are drained from the reactor whilestill hot and, after cooling, are comminuted to granulate or powder, Ingeneral, the reaction products are light resins with softening pointsabove +20° C. some of the resins show a tacky consistency reminiscent ofnatural resins. These properties of the emulsifiers may be desirable inthe production of butadiene-styrene copolymers.

In the production of emulsion polymers comprising large particles, it isimportant to prevent formation of new particles during polymerization.

Formation of new particle in emulsion polymerization does notnecessitate the existence of free micelles; new particles can also beformed when the quantity of emulsifier added is not sufficient forforming new micelles cf, A. S. Dunn in the Article "EmulsionPolymerization", pages 49-50, in Developments in Polymerization, Ed. byR. N. HAWARD, Applied Science Publishers Ltd, 1979).

How latex particles are formed is still not fully known (cf. N.Sutterlin, H. J. Kurth, G. Markert, Makromolekulare Chemie 177,1549-1565 (1976)), more especially page 1550, introduction, sentence 2).

It was neither foreseeable nor to be expected that the reaction productsaccording to the invention are particularly suitable for the productionof large particle size, homodisperse rubber latices, (e.g. polybutadienelatices) particularly where polymerization is carried out at elevatedtemperature in an alkaline medium. On the contrary, saponification andloss of emulsifier properties was expected.

It has now been found that stable, large particle size, homodisperselatices can be produced with the reaction products according to theinvention as emulsifiers and that coagulate formation is no morepronounced than with conventional emulsifiers. Surprisingly, only asmall quantity of emulsifiers according to the invention is required.

Examples of emulsifier acids according to the invention are shown inTable I, numbers 1 to 3, 5 and numbers 7 to 9. They are generallydicarboxylic acids of which the alkali (Li, Na, K, ammonium) salts aresoluble in water and act as emulsifiers in emulsion polymerization. TheNa or K salts are preferably used.

The emulsifier-acids according to the invention are soluble,particularly in powdered form, in aqueous alkali hydroxides. An excessof alkali hydroxide is not necessary for dissolution and should beavoided. However, since the emulsifiers according to the invention aremostly used in combination with potassium peroxodisulfate for thepolymerization of olefinically unsaturated compounds and since protonsare formed during the decomposition of potassium peroxodisulfate, it isadvisable additionally to introduce water-soluble base in such aquantity that the polymerization takes place at pH 8-12 and preferablyat pH 10.5-11.5.

Butadiene, styrene, mixtures of butadiene and styrene, mixtures ofbutadiene and acrylonitrile and sparingly water-soluble acrylates ormethacrylates and also vinyl esters are mentioned in particular asmonomers which may be polymerized to coarsely divided aqueousdispersions using the emulsifiers according to the invention. Inaddition, the new emulsifiers are also suitable for the polymerizationof mixtures of acrylonitrile with styrene and/or α-methyl styrene.Halogen-containing monomers, such as vinyl chloride and chloroprene mayalso be polymerized, in which case polymers of increased particlediameter and improved thermal stability are obtained.

The emulsifiers according to the invention are also suitable for theproduction of graft rubber latices and, in particular, for theproduction of graft rubber latices based on polybutadiene orbutadiene/styrene copolymers or butadiene/acrylonitrile copolymers,suitable graft monomers including, for example., styrene, α-methylstyrene, acrylonitrile, methyl methacrylate or mixtures of thesemonomers, preferably styrene and alcrylonitrile in a ratio by weight of95:5 to 60:40. Graft rubber latices of this type have rubber contents of5 to 95% by weight and preferably 20 to 90% by weight and, after workingup, for example by electrolyte coagulation and drying or by spraydrying, may be converted into graft rubber powders which are suitable,for example, for the production of ABS polymers characterized byexcellent thermal stability. ABS molding compounds of the type inquestion consist, for example, of 10 to 80% by weight and preferably 20to 70% by weight of a graft rubber of styrene and acrylonitrile ormethyl methacrylate on a particulate rubber having an average particlediameter d₅₀ of 0.05 to 2 μm and a rubber content of 20 to 90% by weightand of 90 to 20% by weight and preferably 80 to 30% by weight of athermoplastic resin of 5 to 40 parts by weight acrylonitrile and 95 to60 parts by weight styrene, α-methyl styrene, p-methyl styrene, methylmethacrylate or mixtures thereof.

Large particle size dispersions, more especially polybutadinedispersions, can be produced by standard emulsion polymerizationprocesses. According to the invention, the new emulsifiers are used inthe production of such dispersions. Where particularly homodisperse andlarge particle size latices are to be produced, a seed latex containingonly a little emulsifier is initially introduced and monomers andaqueous emulsifier and initiator-solution is added continuously thereto.

Potassium peroxodisulfate is normally used as initiator, but redoxsystems of organic perioxides, reducing components and heavy metaltraces, preferably in complexed form, may also be used. Otherradical-forming compounds, such as azo-bis-isobutyronitrile andderivatives thereof containing water-solubilizing auxiliary groups, arealso suitable.

                                      TABLE I                                     __________________________________________________________________________                                                      Reaction                                                                      mixture                                                                       solidif-                                                                           Acid                                                                              Acid                  Structural formula                     Molecular                                                                             point                                                                              value                                                                             value              No.                                                                              (not considering isomers)        °C.                                                                       Time                                                                             weight  [°C.]                                                                       calc.                                                                             found              __________________________________________________________________________        ##STR7##                        110                                                                              3  C.sub.28 H.sub.40 O.sub.8                                                     :504.6  50-54                                                                              222.4                                                                             228                    ##STR8##                        110                                                                              3  C.sub.24 H.sub.32 O.sub.8                                                     :448.5  34-36                                                                              250.2                                                                             253                    ##STR9##                        120                                                                              3  C.sub.30 H.sub.40 O.sub.8                                                     :528.6  47-50                                                                              212.3                                                                             220                 4.*                                                                              ##STR10##                       130                                                                              17 C.sub.28 H.sub.28 O.sub.8                                                     :492.5  48-52                                                                              227.9                                                                             200                    ##STR11##                       110                                                                              4  C.sub.20 H.sub.24 O.sub.8                                                     :392.4  21-23                                                                              286 280                 6.*                                                                              ##STR12##                       130                                                                              4  C.sub.20 H.sub.28 O.sub.8                                                     :396.4   7- 10                                                                             283.1                                                                             283                    ##STR13##                       120                                                                              3  C.sub.25 H.sub.34 O.sub.8                                                     :462.5  20-23                                                                              242.6                                                                             250                    ##STR14##                       120                                                                              3  C.sub.22 H.sub.32 O.sub.8                                                     :424.5  50-60                                                                              264.4                                                                             270                    ##STR15##                       120                                                                              3  C.sub.24 H.sub.36 O.sub.8                                                     :452.5  46-50                                                                              248.0                                                                             255                10*                                                                               ##STR16##                       150                                                                              4  C.sub.34 H.sub.54 O.sub.8                                                     :590.8  64-67                                                                              189.9                                                                             203                __________________________________________________________________________     *does not correspond to the invention                                         The reaction temperature and reaction time for the production of the          acidic emulsifier resins are shown in columns 3 and 4                    

EXAMPLES 1 to 36

The acidic emulsifier resins 1 to 3, 5 and 7 to 9 (according to theinvention) and comparison resins 4, 6 and 10 are dissolved in theequivalent quantity, based on the measured acid value, of aqueouspotassium hydroxide and adjusted to a solids content of 5% by weight.These resins are identified in Table I and were produced by meltingtogether one mol of a cycloaliphatic diol and two mols of acycloaliphatic anhydride.

Tables II to V show the polymerization results obtained where variousmonomers (styrene, n-butyl acrylate, vinyl versatate, ethyl acrylate)and various emulsifier resins are used. The average particle diametersd_(T) shown were determined by turbidimetry (see H. Lange Kolloid-Z.Z.Polymere 223, 24-30 (1968)).

The emulsifier resins are less suitable for the polymerization of vinylacetate, vinyl propionate and ethyl acrylate.

The polymerizations were carried out in corked, 500 ml glass bottles,which were rotated in a water bath for 15 hours at 70° C. in protectivebaskets, in the absence of oxygen (purging of the mixtures in thebottles with nitrogen or pure argon). The following recipe was used:

    ______________________________________                                        Water                95.9   parts by weight                                   5% by weight emulsifier solution                                                                   69.7   parts by weight                                   1% Na.sub.2 CO.sub.3 solution                                                                      15.4   parts by weight                                   1% K.sub.2 S.sub.2 O.sub.8 solution                                                                26.1   parts by weight                                   Monomer              87.1   parts by weight                                   Total parts by weight                                                                              294.2  parts by weight.                                  ______________________________________                                    

At complete monomer conversion, latices having a solids content of 30.9%are obtained. In all tests, the emulsifier content is 4%, based on themonomer used, and the initiator content 0.3%, based on monomer.

Tables II to V show that, where emulsifiers of non-invention anhydridesor diols are used, either undesirably finely divided latices areobtained (see tests 4, 9, 13, 18, 22, 27, 31 and 36) or coagulate isformed in very large amounts (see tests 6, 24 and 33). The emulsifiersbased on formulae 1, 2 and 9 (cf. Table I), which lead to largeparticles and are also generally characterized by minimal coagulateformation, proved to be particularly advantageous in the case of styreneand also in the case of butadiene as discussed in the followingExamples.

                  TABLE II                                                        ______________________________________                                        Polymerization of styrene                                                     Ex-              %                      Particle                              am-              Solids   Coagulate                                                                             pH    diameter                              ple  Emulsifier used                                                                           of latex [g]     value d.sub.T (nm)                          ______________________________________                                        1    Di-K-salt of 1                                                                            30.8     0.2     9.3   180                                   2    Di-K-salt of 2                                                                            30.5     0.4     7.9   220                                   3    Di-K-salt of 3                                                                            30.6     <0.1    8.0   100                                    4*  Di-K-salt of 4                                                                            30.5     <0.1    8.1    70                                   5    Di-K-salt of 5                                                                            21.3     10      7.8   360                                    6*  Di-K-salt of 6                                                                            24.5     large   --    --                                                              amount of                                                                     coagulate                                           7    Di-K-salt of 8                                                                            29.5     5.3     9.8   600                                   8    Di-K-salt of 9                                                                            30.4     1.5     9.3   290                                    9*  Di-K-salt of 10                                                                           30.8     <0.1    9.2    70                                   ______________________________________                                         *= does not correspond to the invention                                  

                  TABLE III                                                       ______________________________________                                        Polymerization of n-butyl acrylate                                            Ex-              %                      Particle                              am-              Solids   Coagulate                                                                             pH    diameter                              ple  Emulsifier used                                                                           of latex [g]     value d.sub.T (nm)                          ______________________________________                                        10   Di-K-salt of 1                                                                            30.4     1.3     7.8   130                                   11   Di-K-salt of 2                                                                            30.4     1.1     7.5   160                                   12   Di-K-salt of 3                                                                            30.3     2.0     7.3   110                                    13* Di-K-salt of 4                                                                            30.4     <0.1    7.6    70                                   14   Di-K-salt of 5                                                                            29.3     3.8     7.0   200                                    15* Di-K-salt of 6                                                                            30.0     3.1     6.7   180                                   16   Di-K-salt of 8                                                                            29.3     7.2     7.3   260                                   17   Di-K-salt of 9                                                                            30.1     2.9     7.4   170                                    18* Di-K-salt of 10                                                                           30.7     0.7     8.1    60                                   ______________________________________                                         *= does not correspond to the invention                                  

                  TABLE IV                                                        ______________________________________                                        Polymerization of vinyl versatate                                             Ex-              %                      Particle                              am-              Solids   Coagulate                                                                             pH    diameter                              ple  Emulsifier used                                                                           of latex [g]     value d.sub.T (nm)                          ______________________________________                                        19   Di-K-salt of 1                                                                            26.0     1.7     7.8   110                                   20   Di-K-salt of 2                                                                            26.8     5.3     7.6   800                                   21   Di-K-salt of 3                                                                            26.5     6.1     7.5   370                                    22* Di-K-salt of 4                                                                            30.4     1.8     7.3    80                                   23   Di-K-salt of 5                                                                            coagulate                                                     24* Di-K-salt of 6                                                                            coagulate                                                    25   Di-K-salt of 8                                                                            25.8     21.9    6.2   2200                                  26   Di-K-salt of 9                                                                            28.0     10.6    6.2   1300                                   27* Di-K-salt of 10                                                                           30.2     1.8     8.6   100                                   ______________________________________                                         *= does not correspond to the invention                                  

                  TABLE V                                                         ______________________________________                                        Polymerization of ethyl acrylate                                              Ex-              %                      Particle                              am-              Solids   Coagulate                                                                             pH    diameter                              ple  Emulsifier used                                                                           of latex [g]     value d.sub.T (nm)                          ______________________________________                                        28   Di-K-salt of 1                                                                            29.4     4.5     7.6   170                                   29   Di-K-salt of 2                                                                            28.0     13.5    7.3   210                                   30   Di-K-salt of 3                                                                            28.8     9.6     7.3   160                                    31* Di-K-salt of 4                                                                            30.2     2.6     7.2   100                                   32   Di-K-salt of 5                                                                            28.8     9.9     7.0   340                                    33* Di-K-salt of 6                                                                            26.7     17.6    6.6   420                                   34   Di-K-salt of 8                                                                            26.9     19.4    7.0   470                                   35   Di-K-salt of 9                                                                            26.5     16.7    7.2   270                                    36* Di-K-salt of 10                                                                           30.2     1.4     8.0    80                                   ______________________________________                                         *= does not correspond to the invention                                  

EXAMPLES 37 Seed Latex as Starting Material

A seed latex having an average particle size of approx. 100 nm isrequired for the following Examples. Its production is described in thefollowing:

The following materials are introduced into a 6 liter stainless steelautoclave equipped with an infinitely variable paddle stirrer andinternal temperature control:

    ______________________________________                                        Deionized water           2282.00 g                                           Na salt of disproportionated abietic acid                                                               388.00  g                                           (DRESINATE ® 731), 10% by weight in water                                 Tert.-dodecyl mercaptan, 2.5% by weight                                                                 6.00    g                                           K.sub.2 S.sub.2 O.sub.8 solution in water                                                               155.00  g                                           Potassium hydroxide, solid (high purity)                                                                1.15    g                                           ______________________________________                                    

The autoclave is evacuated and the reduced pressure is equalized withpure nitrogen (3 times). Butadiene is then introduced into there-evacuated autoclave:

    ______________________________________                                        Butadiene           1900.00 g                                                 Rotational speed of the paddle stirrer:                                                           125     r.p.m. [min.sup.-1 ]                              ______________________________________                                    

The mixture is heated to 65° C. and polymerized for about 20 h until thepressure falls to 4 bar. Approx. 4.6 kg of an approx. 40% polybutadienelatex are obtained. The latex has an average particle diameter DAV ofapprox. 100 nm, as determined by the ultracentrifuge technique.

EXAMPLES 38 to 41 Comparison

Preparation of polybutadiene latices by seeded semicontinuouspolymerization having a particle size of approx. 200 nm.

The polybutadiene latex prepared in accordance with Example 37 isinitially introduced as seed latex and butadiene is added thereto insuch a quantity that the average latex particle diameter is aboutdoubled in the polymerization.

The polymerization formulations of Examples 38 to 41 for the variouspolymerization temperatures are shown in Table VI. The mixtures A areinitially introduced, the autoclave is repeatedly evacuated and thevacuum is eliminated with nitrogen. After re-evacuation, butadiene (B)is introduced and the polymerization mixture is heated to the particulartemperature (60° C. or 70° C. or 80° C. or 90° C.).

Emulsifier/activator solution C is added according to the conversion.One third of C is added at a solids content of the latex of 20% byweight, one third at a solids content of 30% by weight and the remainderat a solids content of 40% by weight. The additions may also be morefinely graduated, for example one tenth of C may be added after every 5%increase in the solids content.

The time-solids content relation for this series of tests is shown inTable VII.

It can be seen from Table VII that the polymerization reactions takeplace much more quickly at elevated temperature.

According to M. Morton and P. P. Salatiello (J. Polymer Science, 8,215-224 (1952), cf. page 22), the growth constant K_(w) of thepolymerization of butadiene shows the following dependence ontemperature:

    K.sub.w =1.2·10.sup.8 exp (-9300/R·T) [1·mol.sup.-1 ·sec.sup.-1 ]

Accordingly, the activation energy of the growth reaction is 9300 cal.If the corresponding value in cal (1.986 cal) is used for the gasconstant, the following result is obtained:

    K.sub.w =1.2·10.sup.8 exp (-9300/(1.986·(273.15+° C.))

    ______________________________________                                               Temp. [°C.]                                                                    K.sub.w                                                        ______________________________________                                                0      ˜4                                                              10       8                                                                    20      14                                                                    30      23                                                                    40      38                                                                    50      61                                                                    60      94                                                                    70      142                                                                   80      209                                                                   90      301                                                                   100     425                                                            ______________________________________                                         ##STR17##                                                                     -  (to be compared with K.sub.w of other monomers at 60° C.:           Styrene: 176; Methacrylic Acid Methyl Ester: 367; See: B. Vollert     Grundriβ der Makromol. Chemie, Springer (1962) S. 66).

                                      TABLE VI                                    __________________________________________________________________________    Example No.      38     39     40     41                                      Polymerization temperature                                                                     60     70     80     90                                      __________________________________________________________________________    Deionized water (g)                                                                            957.00 957.00 957.00 957.00                                  KOH, solid (g)   1.72   1.72   1.72   1.72                                    Polybutadiene latex, 35%                                                                       522.00 522.00 522.00 522.00                                  particle diameter 100 nm (g)                                                  Na salt of disproportionated                                                                   73.00  73.00  73.00  73.00                                   abietic acid, aqueous 10%                      A                              solution (g)                                                                  (Dresinate ® 731)                                                         Tert.-dodecyl mercaptan (g)                                                                    4.93   4.93   4.93   4.93                                    K.sub.2 S.sub.2 O.sub.8 solution, 2.5% (g)                                                     164.4  82.2   41.1   20.7                                    (in H.sub.2 O)                                                                Butadiene (g)    1461.0 1461.0 1461.0 1461.0 } B                              Dresinate ® 731:                                                          Na salt of disproportionated                                                                   173.5  173.5  173.5  173.5                                   resinic acid, aqueous 10%                      C                              solution (g)                                                                  K.sub.2 S.sub.2 O.sub.8 solution, 2.5%                                                         --     82.2   123.3  143.7                                   Coagulate (g)    none   none   25     none                                    Solids content % approx. 50%                                                                          approx. 50%                                                                          approx. 50%                                                                          approx. 50%                             pH value         11.1   10.4   11.2   11.2                                    Flow time, DIN 53 211                                                                          21.7   21.4   26.4   24.9                                    [secs.] (4 mm diameter nozzle)                                                LCS diameter [nm] (laser correla-                                                              210    200    198    200                                     tion spectr.)                                                                 DAN              193.3  164    169    139                                     DAL              195.6  171    174    157                                     DAF (see DIN     199.8  177    178    173                                     DAV 53 206)      208.1  181    181    184                                     DVN              196.2  171    173    156                                     DO*              157    95.2   101    80                                      D10              180    153    157    104                                     D20              184    173    172    181                                     D30              186    174    175    189                                     D40              188    178    178    192                                     D50              190    184    181    195                                     D60              193    188    187    196                                     D70              197    190    189    197                                     D80              204    194    193    200                                     D90              223    199    200    206                                     D100             585    218    218    229                                     DAV/DAN          1.08   1.10   1.07   1.32                                    __________________________________________________________________________     *Particle-Size Distribution according to measurements with the                ultracentrifuge (W. Scholtan H. Lange Koll. Z.Z. Polymere, 250, 782-796       (1972)).                                                                 

                  TABLE VII                                                       ______________________________________                                        Time-solids content relation                                                            E = 38    39        40    41                                        Time [h]  60° C.                                                                           70° C.                                                                           80° C.                                                                       90° C.                             ______________________________________                                        1         S =    12.5   14.5    15.8  20.5                                    2                13.6   17.0    20.0  27.5                                    3                15.0   20.0    23.5  34.0                                    4                16.0   23.0    27.5  40.0                                    5                17.5   26.0    31.5  46.5                                    6                18.8   29.0    35.5  49.0                                    7                20.0   32.0    39.0  50.0                                    8                21.6   35.0    38.5                                          9                22.8   38.0    46.5                                          10               24.0   40.5    48.7                                          11               --     --      50.0                                          15               31.0   45.0                                                  20               39.0   48.5                                                  25               44     50.0                                                  32               49.5                                                         ______________________________________                                         E = Example No.                                                               S = solids content in % by weight (latex)                                

Accordingly, an increase in temperature of 10° accelerates the reactionvelocity by a factor of approximately 1.5 for a constant monomerconcentration and radical concentration in the latex particle.

Table VI shows that, starting from the same seed latex in different waysat 60° to 90° C. there are resulting final latices wherein the averagelatex particle diameter is approximately 200 nm.

An attempt to produce final latices with average particle diameters of400 nm from seed latices having an average particle diameter of 100 nmby increasing monomer input, fails as new latex particles are formedwhen the average particle size of approximately 200 nm is reached. Thisis true where DRESINATE® is used as emulsifier and potassiumperoxodisulfate as initiator, the formation of new latex particles beingthe more pronounced, the higher the polymerization temperature and thehigher the amount of emulsifier necessary to prevent the formation ofcoagulate.

EXAMPLES 42 to 49

Efforts for the production of large particle size polybutadiene laticesby semicontinuous seed polymerization.

The polybutadiene latices with particle diameters of approximately 200nm produced in accordance with Examples 38 to 41, Table VI, are used asseed latices (cf. Table VIII, line 6). A same similar polymerizationprocess as in Examples 38 to 41 is applied. The same seed latex is now"enlarged" using the Na salt of disproportionated abietic acid(DRESINATE® 731) and then as a comparison, a preferred emulsifieraccording to the invention (dipotassium salt of the acid of formula 1(cf. Table I) by polymerizing butadiene onto the seed latex. One thirdof the emulsifier-activator solution C is added when the latex solidscontent is 20%, one third when the latex solids content is 30% and theremainder when the latex solids content is 40%.

It can be seen from Table VIII that the amount of coagulate is alwayslower where the emulsifier according to the invention is used than whereDRESINATE® is used.

In addition, particle size determination (by means of ultracentrifugeanalysis of the dispersions) as indicated in Table VII, shows that, theemulsifier according to the invention yields larger average latexparticle diameters and a narrower latex particle diameter distribution.Accordingly, the DAV/DAN ratio of the final latices is closer to 1.0where the emulsifiers according to the invention are used than whereDRESINATE® is used.

                                      TABLE VIII                                  __________________________________________________________________________    Temperature                                                                              60° C.                                                                            70° C.                                                                           80° C.                                                                           90° C.                       Example No.                                                                              42    43** 44   45** 46   47** 48   49**                           __________________________________________________________________________    Deionized water                                                                          973.8*                                                                              973.8                                                                              1052 1052 1052 1052 1052 1052                           KOH, solid 1.72  1.72 1.72 1.72 1.72 1.72 1.72 1.72                           Seed latex Example                                                                       38    38   39   39   40   40   41   41                             35%        504.9*                                                                              504.9                                                                              426.9                                                                              426.9                                                                              426.9                                                                              426.9                                                                              426.9                                                                              426.9                          10% Dresinate 731                                                                        39.6* --   37.6 --   41.0 --   41.7 --                             solution                                                                      10% solution emulsi-                                                                     --    39.6 --   37.6 --   41.0 --   41.7                           fier of formula 1 in                                                          Table I di-K-salt                                                             Tert.-dodecyl                                                                            4.93* 4.93 4.93 4.93 4.93 4.93 4.93 4.93                           mercaptan                                                                     K.sub.2 S.sub.2 O.sub.8 solution,                                                        164.3*                                                                              164.3                                                                              82.2 82.2 41.1 41.1 20.6 20.6                           2.5%                                                                          Butadiene  1467* 1467 1494 1494 1494 1494 1494 1494                           10% Dresinate                                                                            130.3*                                                                              --   147.5                                                                              --   160.8                                                                              --   163.5                                                                              --                             solution                                                                      10% solution emulsi-                                                                     --    130.3                                                                              --   147.5                                                                              --   160.8                                                                              --   164.5                          fier 1, di-K-salt                                                             K.sub.2 S.sub.2 O.sub.8 solution,                                                        --    --   82.2 82.2 123.3                                                                              123.3                                                                              143.7                                                                              143.7                          2.5%                                                                           *All quantities in [g]-                                                       **According to the invention                                                 Coagulate (g)                                                                            43    20   64.5 5.6  101.5                                                                              2.0  69   44                             pH value   11.5  12.0 11   11   10.7 11.0 11.5 12.0                           u = DAV/DAN                                                                              1.41  1.03 1.45 1.04 1.19 1.04 1.29 1.04                           DAN*       174.3 329.5                                                                              130.3                                                                              250.6                                                                              188.3                                                                              296.3                                                                              148.0                                                                              275.2                          DAL        193.9 332.0                                                                              149.0                                                                              253.6                                                                              203.4                                                                              300.2                                                                              162.0                                                                              278.0                          DAF        218.5 334.8                                                                              169.8                                                                              257.0                                                                              215.2                                                                              304.2                                                                              176.4                                                                              281.8                          DAV        245.8 338.2                                                                              188.9                                                                              260.9                                                                              224.2                                                                              308.3                                                                              191.2                                                                              287.2                          DVN        194.7 332.1                                                                              148.8                                                                              253.7                                                                              --   300.2                                                                              --   278.4                          D0 ITGV**  104   270  84   207  102  236  85   219                            D10        136   296  95   224  195  259  127  242                            D20        157   314  117  231  204  271  162  253                            D30        186   322  174  236  207  281  166  263                            D40        209   327  181  242  212  293  169  277                            D50        236   332  191  249  219  312  172  287                            D60        265   337  202  263  227  322  181  294                            D70        293   343  214  278  233  329  198  300                            D80        319   350  228  288  244  337  226  306                            D90        350   364  248  300  275  345  265  314                            D100       407   555  298  785  312  780  353  1600                           __________________________________________________________________________     *Definitions according to DIN 53 206                                          **ITGV -- integral latex particle diameter distribution, as determined by     the ultracentrifuge technique                                                 ***According to the invention                                            

EXAMPLE 50 According to the Invention Polybutadiene Latex, ParticleDiameter d=200 nm

The following materials are introduced in the absence of oxygen into a 6liter stainless steel autoclave (operating pressure up to 20 bar)equipped with an infinitely variable paddle stirrer (150 r.p.m.) andinternal temperature control:

    ______________________________________                                        Deionized water          2282.00 g                                            Emulsifier of formula 1, 50.00   g                                            Table I, di-K-salt                                                            Tert.-dodecyl mercaptan  5.00    g                                            2.5% aqueous potassium peroxodisulfate                                                                 155.00  g                                            solution                                                                      KOH, solid (100%)        1.15    g                                            Butadiene                1650.00 g                                            ______________________________________                                    

The mixture is heated to 65° C. and polymerized for 32 hours untilpressure drops down.

Approx. 4000 g of a coagulate-free 39-40% polybutadiene latex areobtained. The latex can be freed from residual monomers without foamingby distilling off approximately 10% of the water in the latex andreplacing it with deionized water rendered alkaline with KOH to pH 9.

Ultracentrifuge particular size analysis of the latex showed thefollowing particle diameter distribution:

    ______________________________________                                        D0         90      DAN             166.4                                      D10       132      DAL             177.1                                      D20       192      DAF             185.3                                      D30       196      DAV             191.1                                      D40       197      DVN             176.1                                      D50       198                                                                 D60       198                                                                 D70       199                                                                 D80       201      DAV/DAN = 1.15                                             D90       208                                                                 D100      224                                                                 ______________________________________                                    

EXAMPLE 51 According to the Invention Production of a PolybutadieneLatex, Average Particle Diameter DAV 250 nm, by the Continuous AdditionProcess

The following materials are introduced into a 40 liter stainless steelautoclave (operating pressure up to 25 bar) equipped with an infinitelyvariable paddle stirrer (120 r.p.m.) and internal temperature control:

    ______________________________________                                        Deionized water        15350.00 g                                             Potassium hydroxide, solid                                                                           87.50    g                                             Emulsifier resin of formula 1, Table I                                                               332.50   g                                             (finely powdered)                                                             ______________________________________                                    

The pH value of the clear aqueous solution is approximately 11.5.

After repeated evacuation and purging with nitrogen, the autoclave isre-evacuated and a mixture of

    ______________________________________                                        butadiene              2900.00 g                                              tert.-dodecyl mercaptan                                                                              9.00    g                                              ______________________________________                                    

is subsequently introduced. The mixture is heated with stirring to 65°C., after which polymerization is initiated by the introduction underpressure of a solution of

    ______________________________________                                        potassium peroxodisulfate in water, 2.5%                                                                1043.00 g                                           ______________________________________                                    

After a solids content of 6-10% by weight has been reached, a mixture of

    ______________________________________                                        butadiene              8250.00 g                                              tert.-dodecyl mercaptan                                                                              26.00   g                                              ______________________________________                                    

is uniformly introduced over a period of 55 h.

After addition of the butadiene, the mixture is stirred at elevatedtemperature (70° C.) until the pressure has fallen to 4 bar.

The crude latex then has a solids content of approximately 39-40%.

The total polymerization time is approximately 75 hours.

The butadiene still present in the autoclave is largely removed byventing the reactor overhead at approximately 50° C., followed bycondensation, and the crude latex is subjected to steam distillationuntil no more butadiene and divinyl cyclohexene can be detected in thelatex.

The demonomerized latex is freed from slight precipitations byfiltration through 50 μ mesh sieves. It has an average latex particlediameter (DAV of 250 nm, as determined by the ultracentrifuge technique;the polymer has a swelling index of 25 and a gel content of 85%.

EXAMPLE 52 Polybutadiene latex, particle diameter 370 nm (According tothe Invention

The following materials are introduced into a 6 liter stainless steelautoclave corresponding to Example 50:

    ______________________________________                                        Deionized water         2524.0  g                                             Emulsifier of formula 9 (Table I)                                                                     55.0    g                                             dipotassium salt                                                              Tert.-dodecyl mercaptan 5.7     g                                             2.5% aqueous K.sub.2 S.sub.2 O.sub.8 solution                                                         172.0   g                                             KOH, solid (100%)       1.3     g                                             Butadiene               1832.0  g                                             ______________________________________                                    

Polymerization is carried out for 100 hours at 65° C., after which thetemperature has fallen to around 6 bar. A 39% polybutadiene latex havingan average particle diameter DAV of 376 nm is obtained.

    ______________________________________                                        Results of ultracentrifuge analysis:                                          ______________________________________                                        D0         339     DAN             371.2                                      D10        353     DAL             372.1                                      D20        358     DAF             373.5                                      D30        361     DAV             375.7                                      D40        364     DVN             372.3                                      D50        367                                                                D60        370                                                                D70        373     DAV/DAN = 1.01                                             D80        375                                                                D90        383                                                                D100      1000                                                                ______________________________________                                    

EXAMPLE 53 Production of a Polybutadiene Latex, Average ParticleDiameter 350 nm (Seed Inflow Process) (According to the Invention)

The following are introduced in the absence of oxygen into a 40 literstainless steel autoclave (operating pressure up to 25 bar) equippedwith an infinitely variable paddle stirrer (120 r.p.m.) and internaltemperature control:

    ______________________________________                                        Deionzed water           8000.00 g                                            Potassium chloride       30.00   g                                            Emulsifier 1 (Table I), diacid powdered                                                                15.50   g                                            Potassium persulfate K.sub.2 S.sub.2 O.sub.8, solid                                                    10.00   g                                            Caustic potash KOH, solid (100%)                                                                       7.80    g                                            Polybutadiene latex, particle diameter                                                                 507.00  g                                            100 nm, 35% (Example 37)                                                      ______________________________________                                    

The autoclave is evacuated three times, the vacuum being eliminated withnitrogen. After re-evacuation,

    ______________________________________                                        butadiene             3000.00 g                                               n-dodecyl mercaptan   9.00    g                                               ______________________________________                                    

are drawn into the vacuum from a supply vessel.

The mixture is then heated to 60° C. After a latex solids content of 10%has been reached, the following monomer streams are added over a periodof 70 hours:

    ______________________________________                                        Activator-emulsifier inflow (clear solution)                                  Deionized water          7113.00  g                                           Potassium peroxodisulfate K.sub.2 S.sub.2 O.sub.8                                                      30.00    g                                           Emulsifier 1 (Table I) diacid                                                                          180.00   g                                           Caustic potash, KOH, solid                                                                             8.90     g                                           Monomer inflow (homogeneous solution)                                         Butadiene                13000.00 g                                           n-Dodecyl mercaptan      39.00    g                                           ______________________________________                                    

At the beginning of the addition, the polymerization temperature is keptconstant at 70° C. After a polymerization time of approximately 90hours, an approximately 50% polybutadiene latex has formed. There are nosignificant quantities of coagulate either in the autoclave or in thelatex.

The latex can be demonomerized without foaming. The polymer has a gelcontent of approximately 75 to 80% and a swelling index of 25 to 30. Theparticle diameter distribution of the latex is very narrow and the meanparticle diameters are approximately 350 nm, as can be seen from FIG. 1(electron micrograph, contrasting with osmium tetroxide).

The latex, which can also be produced on an industrial scale in thisway, is suitable as a graft base for ABS polymers and other high-impactthermoplastic molding compounds (cf. Example 57).

EXAMPLE 54

Seed inflow process of Example 53 with another emulsifier according tothe invention.

The procedure is as in Example 53, except that the emulsifier describedthere is replaced by the same quantity in grams of an emulsifier havingthe idealized structure 7 in Table I in the form of the dipotassiumsalt.

After a polymerization time of approximately 100 hours, an approximately50% polybutadiene latex has formed. Its particle size distribution wasdetermined by the ultracentrifuge technique:

    ______________________________________                                        D0         334     DAN             418.6                                      D10        393     DAL             422.0                                      D20        398     DAF             427.0                                      D30        402     DAV             435.4                                      D40        406     DVN             422.5                                      D50        410     DAV/DAN = 1.04                                             D60        415                                                                D70        422                                                                D80        432                                                                D90        490     DAV/DAN = 1.04                                             D100      1000                                                                ______________________________________                                    

The polymer has a gel content of 70% and a swelling index of 30.

This latex is also eminently suitable as a graft base for the productionof high-impact molding compounds.

EXAMPLE 55 Seed Inflow Polymerization Process Using an EmulsifierAccording to the Invention and a Redox Initiator System

The following are introduced into an autoclave corresponding to Example53:

    ______________________________________                                        Deionized water       8000.00                                                 Emulsifier of formula 1 in Table I,                                                                 15.50                                                   diacid, powdered                                                              Potassium hydroxide, solid, 100%                                                                    3.50            A                                       Polybutadiene latex, particle diameter                                                              507.00                                                  100 nm (Example 37)                                                           Storage vessel I                                                               Butadiene             1500.00                                                                                      B                                       n-Dodecyl mercaptan   9.00                                                    Storage vessel II                                                              Butadiene             1500.00                                                                                      C                                       p-Menthane hydroperoxide, 50%                                                                       7.00                                                    Storage vessel III                                                            Deionized water       490.00                                                  Sodium formaldehyde sulfoxylate                                               (Rongalit C ®), solid                                                                           1.50            D                                       Fe(II))-ethylenediamine tetraacetic acid                                                            5.00                                                    complex, 0.05 molar solution in water                                         Storage vessel IV                                                             Deionized water       6623.00                                                 Rongalit C ®, solid                                                                             4.50                                                    Emulsifier acid of formula 1, Table I                                                               170.60          E                                       KOH, solid            38.60                                                   Storage vessel V                                                               Butadiene             8654.00                                                                                      F                                       n-Dodecyl mercaptan   39.00                                                   Storage vessel VI                                                              Butadiene             4347.00                                                                                      G                                       p-Menthane hydroperoxide, 50%                                                                       29.80                                                   ______________________________________                                    

After mixture A has been introduced, the autoclave is repeatedlyevacuated and the pressure equalized with nitrogen. After re-evacuation,mixtures B and C are drawn in.

The autoclave is heated to an internal temperature of 70° C., afterwhich D is added.

After a solids content in the crude latex of approximately 7 has beenreached, streams E, F and G are introduced into the reactor over periodsof 70 hours, 55 hours and 60 hours, respectively.

After a polymerization time of 100 hours, the polymerization reaction isterminated, the crude latex is vented and demonomerized.

The latex particle diameter distribution of the coagulate-free,demonomerized latex appears as follows:

    ______________________________________                                        D0         219       DAN           389                                        D10        374       DAL           391                                        D20        378       DAF           393                                        D30        382       DAV           395                                        D40        386       DVN           391                                        D50        389                                                                D60        393                                                                D70        397                                                                D80        402       DAV/DAN       1.015                                      D90        412                                                                D100      1100                                                                ______________________________________                                    

The latex is eminently suitable as a graft base for the production ofABS polymers and other high-impact thermoplastics and shows furtherimproved thermal stability compared with persulfate activation.

EXAMPLE 56 Comparison

The procedure is as in Example 53 except that, instead of the emulsifieraccording to the invention, the same quantity (in g) of DRESINATE®731 isused.

After a polymerization time of approximately 80 hours, the pressure hasfallen to around 3.5 bar and a latex having the following particle sizedistribution has formed:

    ______________________________________                                        D0        117.5    DAN              170.5                                     D10       144      DAL              179.2                                     D20       156      DAF              190.2                                     D30       165      DAV              203.2                                     D40       174      DVN              179.8                                     D50       183                                                                 D60       196                                                                 D70       233                                                                 D80       268      DAV/DAN = 1.19                                             D90       285                                                                 D100      326                                                                 ______________________________________                                    

The latex has a gel content of approximately 95% and a swelling index ofapproximately 20. The latex is unsuitable as a graft base for theproduction of ABS polymers because the strength values of ABS moldingsproduced therewith are inadequate.

FIG. 2 shows the evolution of the average latex particle diameter as afunction of time on the basis of quasicontinuous measurements. Startingfrom the same seed latex, the particle size develops differently wherethe emulsifier according to the invention is used than where Dresinateis used.

The measurements were performed by laser correlation spectroscopy. Thelatex particle diameter determined by laser correlation spectroscopy islarger by a factor of 1.2 than the particle diameter determined byelectron microscopy or by the ultracentrifuge technique.

Particulars of the on-line measurement of latex particles can be found,for example, in DE-OS 3 303 337.

EXAMPLE 57 According to the Invention Graft Polymerization of aStyrene/Acrylonitrile Mixture onto the Polybutadiene Latex of Example 53

50 Parts by weight polybutadiene (in the form of a latex having a solidscontent of 25% by weight prepared by dilution of the polybutadiene latexof Example 53 with deionized water) are heated under nitrogen to 63° C.,followed by the addition of 0.5 part by weight K₂ S₂ O₈ (dissolved in 15parts by weight water). A mixture of 36 parts by weight styrene and 14parts by weight acrylonitrile and also 1.5 parts by weight of the sodiumsalt of disproportionated abietic acid (dissolved in 25 parts by weightwater)) is then introduced over a period of 4 hours during which thegrafting reaction takes place. Following an after-reaction time, thelatex is coagulated in a magnesium sulfate/acetic acid solution and theresulting powder is dried in vacuo at 70° C.

EXAMPLE 58 According to the Invention

Testing of a mixture of the graft polymer described in Example 57 with astyrene/acrylonitrile copolymer and an α-methyl styrene/acrylonitrilecopolymer.

The graft polymer described in Example 57 was mixed in an internalkneader with a styrene/acrylonitrile copolymer (72:28, M_(w) approx.115,000, M_(w) M_(n) -1≦2) or with an α-methyl styrene/acrylonitrilecopolymer (72:28, M_(w) approx. 75,000, M_(w) /M_(n) -1≦1) in the ratiosby weight shown in Table IX. 2 Parts by weight pentaerythritoltetrastearate and 0.1 part by weight of a silicone oil (based in eachcase on 100 parts by weight graft polymer+copolymer) were used asadditives. After processing by injection molding, impact strength (DIN53 453), hardness (DIN 53 456), Vicat B softening point (DIN 53 460),MVI (DIN 53 735u) and also natural color (after processing at 240° C. to280° C.) and surface gloss (according to DE-AS 2 420 358) weredetermined, the results being shown in Table IX.

                                      TABLE IX                                    __________________________________________________________________________    Testing of the graft rubber described in Example 57                                          α-methyl                                                        Styrene/                                                                              styrene/                                                       Graft poly-                                                                          acryloni-                                                                             acryloni-                                                      mer of Exam-                                                                         trile copolymer                                                                       trile copolymer                                                                       RT   -40° C.                                                                          Vicat                                                                             MVI                                 ple 57 [parts                                                                        [parts by                                                                             [parts by                                                                             a.sub.k                                                                            a.sub.k                                                                            Hc   B   [cm.sup.3 /                                                                        Gloss Natural color            by weight]                                                                           weight] weight] [kJ/m.sup.2 ]                                                                      [kJ/m.sup.2 ]                                                                      [n/mm.sup.2 ]                                                                      [°C.]                                                                      10 mins.]                                                                             240° C.                                                                    260°                                                                       280°         __________________________________________________________________________                                                              C.                  30     70      --      15.3 9.4  103  102 8.0  F-G                                                                              --  --  --                  40     60      --      16.8 12.3 84   100 5.9  F  light                                                                             light                                                                             light               50     50      --      17.2 14.6 67    96 4.1  F  --  --  --                  20     --      80      10.4 5.5  113  115 2.0  F  --  --  --                  30     --      70      13.9 7.6  93   113 1.6  F  --  --  --                  40     --      60      16.7 10.3 77   109 1.2  E-F                                                                              light                                                                             light                                                                             yellowish           __________________________________________________________________________

EXAMPLES 59 According to the Invention Graft Polymerization of aStyrene/Acrylonitrile Mixture onto the Polybutadiene latex of Example 53

The procedure was as described in Example 57 except that, instead of thesodium salt of disproportionated abietic acid, 1.5 parts by weight ofcompound 1 in Table I in the form of the dipotassium salt was used asemulsifier in the graft reaction.

EXAMPLE 60 According to the Invention Testing of a Mixture of the GraftPolymer Described in Example 59 with a Styrene/Acrylonitrile Copolymerand an α-Methyl Styrene/Acrylonitrile Copolymer

The resin components described in Example 58 were used and the resultsare shown in Table X.

                                      TABLE X                                     __________________________________________________________________________    Testing of the graft rubber described in Example 59                                          α-methyl                                                        Styrene/                                                                              styrene/                                                       Graft poly-                                                                          acryloni-                                                                             acryloni-                                                      mer of Exam-                                                                         trile copolymer                                                                       trile copolymer                                                                       RT   -40° C.                                                                          Vicat                                                                             MVI                                 ple 59 [parts                                                                        [parts by                                                                             [parts by                                                                             a.sub.k                                                                            a.sub.k                                                                            Hc   B   [cm.sup.3 /                                                                        Gloss Natural color            by weight]                                                                           weight] weight] [kJ/m.sup.2 ]                                                                      [kJ/m.sup.2 ]                                                                      [n/mm.sup.2 ]                                                                      [°C.]                                                                      10 mins.]                                                                             240° C.                                                                    260°                                                                       280°         __________________________________________________________________________                                                              C.                  30     70      --      16.1 9.3  103  103 8.2  F-G                                                                              --  --  --                  40     60      --      17.1 13.0 85   101 5.8  F  very                                                                              very                                                                              light                                                                 light                                                                             light                   50     50      --      17.6 14.0 67    95 4.0  F  --  --  --                  20     --      80      10.5 6.3  114  115 2.2  F  --  --  --                  30     --      70      13.5 8.1  95   113 1.7  F  --  --  --                  40     --      60      16.9 10.0 76   108 1.2  E-F                                                                              very                                                                              very                                                                              light                                                                 light                                                                             light                   __________________________________________________________________________

EXAMPLE 61 According to the Invention Graft Polymerization of aStyrene/Acrylonitrile Mixture onto the Polybutadiene Latex of Example 56

50 Parts by weight polybutadiene (in the form of a latex having a solidscontent of 25% by weight prepared by dilution of the polybutadiene latexof Example 56 with deionized water) are heated under nitrogen to 63° C.,followed by the addition of 0.5 part by weight K₂ S₂ O₈ (dissolved in 15parts by weight water). A mixture of 36 parts by weight styrene and 14parts by weight acrylonitrile and also 2 parts by weight of compound 1in Table I in the form of the dipotassium salt (dissolved in 25 parts byweight water) is then added over a period of 4 hours during which thegraft reaction takes place. Following an after-reaction time, the latexis coagulated in a magnesium sulfate/acetic acid solution and theresulting powder is dried in vacuo at 760° C.

EXAMPLE 62 According to the Invention Testing of a Mixture of the GraftPolymer Described in Example 61 with a Styrene/Acrylonitrile Copolymerand an α-Methyl Styrene/Acrylonitrile Copolymer

The components described in Example 58 were used in the quantities shownin Table XI which also shows the natural colors after processing at 240°C. to 280° C.

                                      TABLE XI                                    __________________________________________________________________________    Testing of the graft rubber described in Example 61                           Graft polymer                                                                          Styrene/acrylo-                                                                        α-methyl styrene/                                     of Example 61                                                                          trile copolymer                                                                        acrylonitrile copolymer                                                                   Natural color                                   [parts by weight]                                                                      [parts by weight]                                                                      [parts by weight]                                                                         240° C.                                                                    260° C.                                                                    280° C.                          __________________________________________________________________________    40       60       --          light                                                                             light                                                                             light                                   30       --       70          light                                                                             light                                                                             yellowish                               __________________________________________________________________________

EXAMPLE 63 Comparison Graft Polymerization of a Styrene/AcrylonitrileMixture onto the Polybutadiene Latex of Example 56

The procedure is as described in Example 1 except that, instead of thedipotassium salt of compound 1 in Table I, 2 parts by weight of thesodium salt of disproportionated abietic acid were used as emulsifier inthe graft reaction.

EXAMPLE 64 Comparison Testing of a mixture of the graft polymerdescribed in Example 63 with a Styrene/Acrylonitrile Copolymer and anα-Methyl Styrene/Acrylonitrile Copolymer

The components described in Example 58 were used in the quantities shownin Table XII which also shows the natural colors after processing attemperatures of 240° C. to 280° C.

                                      TABLE XII                                   __________________________________________________________________________    Testing of the graft rubber described in Example 63                           Graft polymer                                                                          Styrene/acrylo-                                                                        α-methyl styrene/                                     of Example 63                                                                          trile copolymer                                                                        acrylonitrile copolymer                                                                   Natural color                                   [parts by weight]                                                                      [parts by weight]                                                                      [parts by weight]                                                                         240° C.                                                                    260° C.                                                                     280° C.                         __________________________________________________________________________    40       60       --          light                                                                             light                                                                              yellowish                              30       --       70          light                                                                             yellow-                                                                            yellow                                                                   ish                                         __________________________________________________________________________

We claim:
 1. Rubber latices comprising rubber latex particles and anemulsifier wherein the emulsifier is a reaction product of 1 of acycloaliphatic diol corresponding to formula 1

    HO--R--OH                                                  I

with 2 mols of cycloaliphatic carboxylic anhydrides corresponding toformulae II, III or a mixture thereof ##STR18## in which R is acycloaliphatic hydrocarbon radical containing 6 to 20 carbon atoms towhich the hydroxy groups are attached directly or via methylene groupand X represents ##STR19## chemical bond which reaction products areobtained by fusion of the cycloaliphatic diol and of the cycloaliphaticcarboxylic anhydride in an inert gas atmosphere at temperatures of from100° C. to 250° C., and the alkali and ammonium salts of these reactionproducts.
 2. Graft rubber latices obtained by polymerization of mixturesof styrene and acrylonitrile in the presence of polybutadiene,containing the reaction product according to claim 1 as emulsifiers. 3.ABS molding compounds consisting of 10 to 80% by weight of a graftrubber of styrene and alcrylonitrile on a particulate rubber and 90 to20% weight of a thermoplastic resin of 5 to 40 parts by weightacrylonitrile and 95 to 60 parts by weight styrene, α-methyl styrene,p-methyl styrene, methyl methacrylate or mixtures thereof,wherein thereaction product according to claim 1 constitute the emulsifier used forthe production of the graft rubber.